M. Tamm, K. Baum, T. Lügger, R. Fröhlich, K. Bergander
FULL PAPER
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[(o-Ph2PC6H4-η6-C7H7)Mo(CO)2(P؊Mo)] (4): The phosphane 2 29.4 Hz, C-8), 141.5 (d, JC,P ϭ 45.3 Hz, C-9), 134.5 (d, JC,P
(9.72 g, 28.58 mmol) and Mo(CO)6 (7.65 g, 28.98 mmol) were dis-
ϭ
ϭ
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42.1 Hz, i-C), 134.2 (d, JC,P ϭ 12.1 Hz, o-C), 132.7 (d, JC,P
solved in methylcyclohexane (250 mL) and slowly heated to 120 °C 37.7 Hz, i-C), 132.2 (s, C-10), 131.6 (d, 2JC,P ϭ 12.1 Hz, o-C), 130.6
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within 2 h. Heating was continued at this temperature while stirring
(d, JC,P ϭ 1.9 Hz, C-12), 130.5 (d, JC,P ϭ 2.6 Hz, p-C), 129.8 (d,
for 10 h. The solvent and unchanged Mo(CO)6 were removed in 4JC,P ϭ 1.9 Hz, p-C), 129.1 (d, JC,P ϭ 5.8 Hz, C-11), 128.5 (d,
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vacuo, and the residue was recrystallized from dichloromethane/
3JC,P ϭ 9.6 Hz, m-C), 128.3 (d, JC,P ϭ 10.2 Hz, m-C), 127.5 (d,
hexane at 0 °C. After 12 h, 4 was isolated as a red crystalline solid 3JC,P ϭ 9.6 Hz, C-13), 107.3 (d, JC,P ϭ 2.2 Hz, C-1), 99.4 (d,
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by filtration. Yield: 8.84 g (64%) Ϫ H NMR (CD2Cl2, 600 MHz):
JC,P ϭ 1.3 Hz, C-3), 99.2 (s, C-2), 98.5 (d, JC,P ϭ 5.3 Hz, C-4), 93.6
δ ϭ 7.66 (m, 2 H, o-C6H5), 7.47 (dd, 1 H, 13-H), 7.42 (m, 6 H, (d, JC,P ϭ 5.1 Hz, C-5), 89.5 (s, C-7), 80.9 (s, C-6). 31P NMR
C6H5), 7.38 (m, 3 H, C6H5 ϩ 12-H), 7.31 (t, 1 H, 11-H), 7.27 (t, 1 (CDCl3, 81 MHz): δ ϭ 49.1. MS (EI): m/z (%) ϭ 527 (11) [M Ϫ
H, 10-H), 5.97 (t, 1 H, 3-H), 5.53 (t, 1 H, 4-H), 5.22 (t, 1 H, 5-H), CO]ϩ, 447 (9) [M Ϫ CO Ϫ Br]ϩ. IR (KBr): ν(CO) ϭ 1946 cmϪ1
.
4.77 (d, 1 H, 2-H), 2.62 (dd, 1 H, 7-endo-CH2), 2.35 (dd, 1 H, 7-
IR (CH2Cl2): ν(CO) ϭ 1956 cmϪ1. C26H20BrMoOP (555.26): calcd.
exo-CH2), 2.12 (tt, 1 H, 6-H). 13C NMR (CD2Cl2, 150.7 MHz): C 56.24, H 3.63; found C 55.30, H 3.64.
δ ϭ 227.2 (d, 2JC,P ϭ 10.2 Hz, CO), 223.9 (d, 2JC,P ϭ 12.1 Hz, CO),
[(o-Ph2PC6H4-η7-C7H6)MoBr2(P؊Mo)] (7):
A
solution of
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153.6 (d, JC,P ϭ 27.5 Hz, C-8), 151.3 (d, JC,P ϭ 40.9 Hz, C-9),
(4.92 g, 8.86 mmol) in dichloromethane (120 mL) was treated with
a solution of bromine (0.24 mL, 4.68 mmol) in dichloromethane
(10 mL) at 0 °C, and the resulting mixture was subsequently stirred
for 1 h at ambient temperature. The solution was reduced in volume
to about 50 mL and added dropwise to rapidly stirred hexane to
precipitate 7, which was isolated as a brown, crystalline solid by
filtration, washing with hexane and drying in vacuo. Purification
was possible by recrystallization from dichloromethane to afford
crystals of 7·CH2Cl2. Yield: 5.30 g (86%). 31P NMR (CDCl3,
81 MHz): δ ϭ 38.5. MS (EI): m/z (%) ϭ 607 (16) [Mϩ], 527 (68)
[M Ϫ Br]ϩ, 448 (21) [M Ϫ 2 Br]ϩ. C26H22Br2Cl2MoP (692.09):
calcd. C 45.12, H 3.20; found C 45.72, H 3.13.
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142.0 (d, JC,P ϭ 36.4 Hz, i-C6H5), 138.1 (d, JC,P ϭ 40.2 Hz, i-C),
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133.4 (s, C-10), 133.1 (d, JC,P ϭ 12.8 Hz, o-C), 132.8 (d, JC,P
ϭ
11.5 Hz, o-C), 130.3 (s, C-12), 129.8 (s, p-C), 129.6 (s, p-C), 128.7
(d, 3J ϭ 9.6 Hz, m-C), 128.4 (d, 3J ϭ 10.1 Hz, m-C), 127.4 (d, 3J ϭ
12.8 Hz, C-13), 127.3 (d, 3J ϭ 5.8 Hz, C-11), 104.7 (s, C-5), 98.8
(s, C-2), 90.9 (s, C-3), 86.3 (s, C-4), 86.0 (s, C-1), 54.8 (s, C-6), 33.6
(s, CH2-7). 31P NMR (CDCl3, 81 MHz): δ ϭ 64.5. MS (EI): m/z
(%) ϭ 504 (12) [Mϩ], 476 (4) [M Ϫ CO]ϩ, 448 (100) [M Ϫ 2 CO]ϩ.
IR (KBr): ν(CO) ϭ 1905 (shoulder), 1889, 1873, 1816 cmϪ1
.
C27H21MoO2P (504.38): calcd. C 64.30, H 4.20; found C 64.90,
H 4.30.
[(o-Ph2PC6H4-η7-C7H6)Mo(CO)2(P؊Mo)]BF4 (5): A solution of 4
(8.84 g, 17.53 mmol) in dichloromethane (200 mL) was treated with
(Ph3C)BF4 (5.20 g, 15.75 mmol) at 0 °C, and the resulting mixture
was subsequently heated to reflux for 30 min. The solution was
reduced in volume to about 50 mL and added dropwise to rapidly
stirred diethyl ether at 0 °C to precipitate 5, which was isolated as
an orange crystalline solid by filtration, washing with diethyl ether
and drying in vacuo. Yield: 8.34 g (90%). 1H NMR (CD2Cl2,
600 MHz): δ ϭ 7.88 (dd, 1 H, 13-H), 7.71 (t, 1 H, 12-H), 7.59 (t,
1 H, 11-H), 7.55Ϫ7.59 (m, 6 H, p- ϩ m-C6H5), 7.43Ϫ7.39 (m, 4 H,
o-C6H5), 7.38 (t, 1 H, 10-H), 6.06 (m, 2 H, 3,6-H), 6.00 (m, 2 H,
4,5-H), 5.59 (dd, 2 H, 2,7-H). 13C NMR (CD2Cl2, 150.7 MHz): δ ϭ
[(o-Ph2PC6H4-η7-C7H6)Mo(CH2SiMe3)Br(P؊Mo)] (8): A solution
of 7·CH2Cl2 (200 mg, 0.29 mmol) in THF (20 mL) was treated with
Me3SiCH2MgCl (0.3 mL of a 1.0 solution in diethyl ether,
0.3 mmol) at Ϫ78 °C, and the resulting mixture was allowed to
warm to room temperature and was subsequently stirred for 12 h
at ambient temperature. The solvent was evaporated, and the res-
idue was extracted with hexane (20 mL). Keeping the filtrate in the
refrigerator for 24 h at 0 °C afforded orange crystals of 8. Yield:
110 mg (62%). 31P NMR (CDCl3, 81 MHz):
δ ϭ 51.9.
C29H31BrMoPSi (614.47): calcd. C 56.69, H 5.09; found C 56.97,
H 5.11.
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[(o-Ph2PC6H4-η7-C7H6)Mo(CH2SiMe3)2(P؊Mo)] (9): A solution
of 7·CH2Cl2 (500 mg, 0.72 mmol) in THF (20 mL) was treated with
a large excess of Me3SiCH2MgCl (7.2 mL of a 1.0 solution in
diethyl ether, 7.2 mmol) at Ϫ78 °C, and the resulting mixture was
allowed to warm to room temperature and was subsequently stirred
for 12 h at ambient temperature. The solvent was evaporated, and
the residue was extracted with hexane (20 mL). Purification was
possible by column chromatography on silica using diethyl ether/
petroleum ether (1:1) as eluent to isolate 8 as an orange-yellow,
crystalline solid. Yield: 420 mg (93%). 31P NMR (CDCl3, 81 MHz):
δ ϭ 54.6. C33H42MoPSi2 (621.78): calcd. C 63.75, H 6.81; found C
63.35, H 6.74.
212.6 (d, JC,P ϭ 25.3 Hz, CO), 146.7 (d, JC,P ϭ 25.5 Hz, C-8),
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141.5 (d, JC,P ϭ 47.3 Hz, C-9), 133.3 (s, C-10), 132.8 (d, JC,P
ϭ
ϭ
ϭ
ϭ
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2.6 Hz, C-12), 132.3 (d, JC,P ϭ 12.1 Hz, o-C), 132.1 (d, JC,P
47.2 Hz, i-C), 132.0 (d, JC,P ϭ 2.6 Hz, p-C), 131.0 (d, JC,P
6.4 Hz, C-11), 129.9 (d, JC,P ϭ 10.9 Hz, m-C), 127.3 (d, JC,P
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11.5 Hz, C-13), 126.7 (d, JC,P ϭ 3.2 Hz, C-1), 98.2 (s, C-3,6), 96.0
(s, C-4,5), 94.7 (d, JC,P ϭ 3.6 Hz, C-2,7). 31P NMR (CDCl3,
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81 MHz): δ ϭ 59.9. MS (ESI): m/z (%) ϭ 503 (100) [M Ϫ BF4]ϩ.
IR (KBr): ν(CO) ϭ 2032, 1988 cmϪ1. IR (CH2Cl2): ν(CO) ϭ 2035,
1994 cmϪ1. C27H20BF4MoO2P (590.17): calcd. C 54.95, H 3.42;
found C 54.16, H 3.48.
[(o-Ph2PC6H4-η7-C7H6)Mo(CO)Br(P؊Mo)] (6): A solution of 5
(2.40 g, 4.07 mmol) in acetone (160 mL) was treated with NaBr X-ray Crystallography:[37,54] Data sets were collected at Ϫ75 °C (for
(3.04 g, 29.55 mmol), and the resulting mixture was subsequently 2, 4, and 5) with an EnrafϪNonius KappaCCD or at Ϫ120 °C (for
heated to reflux for 14 h. After evaporation of the solvent, the res-
idue was transferred to a silica chromatography column. Elution
6Ϫ9) with a Bruker AXS APEX diffractometer both equipped with
˚
a rotating anode using Mo-Kα radiation (λ ϭ 0.71073 A). Empir-
with dichloromethane produced a green band that was collected to
ical absorption correction with SORTAV[55] (for 2, 4, and 5) or
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give 6 as a green, crystalline solid. Yield: 0.72 g (35%). H NMR SADABS[56] (for 6Ϫ9) was applied to the raw data. Structure solu-
(CD2Cl2, 600 MHz): δ ϭ 7.79 (dd, 1 H, 13-H), 7.71 (dd, 2 H, o- tion was performed in all cases with SHELXS[57] and refinement
C6H5), 7.53 (t, 1 H, 12-H), 7.47 (t, 1 H, 11-H), 7.44 (t, 1 H, 10-H), with SHELXL[58] with anisotropic thermal parameters for all
7.43Ϫ7.33 (m, 6 H, p- ϩ m-C6H5), 7.20 (dd, 2 H, o-C6H5), 5.80 (t,
atoms. Hydrogen atoms were added to the structure models on
1 H, 5-H), 5.66 (d, 1 H, 2-H), 5.42 (t, 1 H, 4-H), 5.40 (t, 1 H, 3- calculated positions and were refined as riding atoms (2, 4, and 5)
H), 5.07 (t, 1 H, 6-H), 4.42 (d, 1 H, 7-H). 13C NMR (CD2Cl2, or are unrefined for 6, 7, and 9. Hydrogen atoms for 8 were located
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150.7 MHz): δ ϭ 232.3 (d, 2JC,P ϭ 15.6 Hz, CO), 150.4 (d, JC,P
ϭ
in the difference Fourier map and were refined with isotropic ther-
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Eur. J. Inorg. Chem. 2002, 918Ϫ928